WO1994003417A1 - Procede d'isomerisation de 1,1,2-trichlorotrifluorethane - Google Patents

Procede d'isomerisation de 1,1,2-trichlorotrifluorethane Download PDF

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Publication number
WO1994003417A1
WO1994003417A1 PCT/US1993/006824 US9306824W WO9403417A1 WO 1994003417 A1 WO1994003417 A1 WO 1994003417A1 US 9306824 W US9306824 W US 9306824W WO 9403417 A1 WO9403417 A1 WO 9403417A1
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WO
WIPO (PCT)
Prior art keywords
isomerization
catalyst
aici
cci
per
Prior art date
Application number
PCT/US1993/006824
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English (en)
Inventor
William Henry Gumprecht
William Joel Huebner
Mario Joseph Nappa
Original Assignee
E.I. Du Pont De Nemours And Company
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Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to DE69314644T priority Critical patent/DE69314644T2/de
Priority to JP50535094A priority patent/JP3322402B2/ja
Priority to EP93918272A priority patent/EP0652857B1/fr
Publication of WO1994003417A1 publication Critical patent/WO1994003417A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation

Definitions

  • This invention relates to processes using activated aluminum trichloride catalysts and more particularly to chlorofluorocarbon isomerizations in the presence of such catalysts.
  • Chlorofluorocarbons have been widely used as refrigerants and aerosols. Concerns have developed over the release of various chlorofluorocarbons into the atmosphere. Efforts have already begun to eliminate any widespread emission of CCI2F 2 (CFC-12) and CCI 3 F (CFC-11) due to their ability to reach the stratosphere intact. In recent years, increased attention has focused on use of perfluorocarbons, hydrofluorocarbons and hydrochloro- fluorocarbons which are considered to have significantly lower potential for contributing to ozone depletion. Of particular interest to the refrigerant industry is the hydrofluorocarbon 1,1,1,2-tetrafluoroethane (HFC-134a) .
  • HFC-134a hydrofluorocarbon 1,1,1,2-tetrafluoroethane
  • HFC-134a can be derived from the intermediates 1,1,1- trichlorotrifluoroethane (CFC-113a) and 1,1,1,2-tetra- fluorodichloroethane CFC-114a) .
  • These intermediates are, in turn, t e iso ers of the readily available and chemically more symmetric chlorofluoroethanes, 1,1,2- trichlorotrifluoroethane (CFC-113) and 1,1,2,2-tetra- fluorodichloroethane (CFC-114) , respectively.
  • the isomerization of these more symmetric chlorofluoroethanes by treatment with aluminum trichloride is well documented in the art. For example, U.S. Pat. No.
  • 4,925,993 discloses a process for isomerizing CFC-112 (i.e., CCI 2 FCCI 2 F) to CFC-112a (i.e., CCI3CCIF2) or CFC-113 to CFC-113a by contacting the CFC-112 or CFC-113 with an activated aluminum trichloride catalyst.
  • the catalyst is prepared by contacting the chlorofluorocarbon with anhydrous aluminum trichloride in the presence of selected metals. Reportedly, the amount of non-isomerized chlorofluoro- ethane in the product mixture can be held to less than 450 ppm, and the catalyst can be used for eighteen cycles.
  • High purity CFC-113a is an advantageous starting material for the preparation of high purity 1,1,1,2- tetrafluoroethane (HFC-134a) . More particularly, CFC-113a may be reacted with HF to afford CFC-114a which in turn may be hydrodechlorinated to HFC-134a. Unless an isomer separation process is employed, the presence of substantial amounts CFC-113 in the starting material •would eventually lead to the production of a HFC-134a product containing significant amounts of 1,1,2,2- tetrafluoroethane (HFC-134) . It has been found that for many applications, the presence of significant amounts of HFC-134 in an HFC-134a product can alter the physical and chemical properties of the product. Thus, there is interest in developing more efficient isomerization methods for obtaining CFC-113a products with negligible amounts (i.e., less than about 500 ppm) of non- isomerized starting material.
  • the invention provides an isomerization process for producing a desirable chlorofluoroethane intermediate of 1,1, 1,2-tetrafluoroethane.
  • the process comprises (1) activating a micropulverized anhydrous aluminum trichloride which has a surface area of greater than about 0.8 m 2 /g by treating it with at least about 10 g per g of aluminum trichloride of CCI 2 FCCIF 2 with agitation; and (2) isomerizing an additional amount of CCI2FCCIF 2 by (i) mixing said additional amount of CCI 2 FCCIF 2 with said activated catalyst with agitation to provide an initial degree of isomerization, and (ii) cooling the mixture of chlorofluorocarbons and catalyst to a temperature of about 20°C with agitation, to provide a product containing CCI 3 CF 3 .
  • the amount of non-isomerized CCI 2 FCCIF 2 in the product is generally less than about 400 ppm.
  • Figure 1 is a plot of non-isomerized CFC-113 in CFC-113a product as a function of isomerization cycle for catalyst prepared from AICI 3 having a surface area of about 0.27 m 2 /g.
  • Figure 2 is a plot of non-isomerized CFC-113 in CFC-113a product as a function of isomerization cycle for catalyst prepared from AICI 3 having a surface area of about 0.39 m 2 /g.
  • Figure 3 is a plot of non-isomerized CFC-113 in CFC-113a product as a function of isomerization cycle for catalyst prepared from AICI 3 having a surface area of about 0.85 m 2 /g.
  • Figure 4 is a plot of non-isomerized CFC-113 in CFC-113a product as a function of isomerization cycle for catalyst prepared from micropulverized AICI 3 having a surface area of about 0.95 m 2 /g. DETAILED DESCRIPTION
  • This invention provides catalytic isomerization of CCI2FCCIF2 starting materials.
  • the process uses advantageous activated AICI 3 catalysts.
  • the isomerization catalyst may be activated in situ (i.e., in the same reactor used for isomerization) by treating micropulverized anhydrous aluminum trichloride with CCI2FCCIF2. Agitation (e.g., stirring) should be provided during treatment.
  • Micropulverization involves mechanical comminution and may be practiced using a conventional operation such as crushing, ball milling. rod milling or grinding.
  • the micropulverized anhydrous aluminum trichloride has the following properties: a particle size such that greater than 80% of the material passes through a 100 mesh screen (sieve opening of 0.149 mm); less than 30 ppm iron; less than
  • the AICI 3 should have a surface area greater than about 0.8 m 2 /g (as measured by the well known single-point BET method using nitrogen, for example, a gas mixture of 30% nitrogen and 70% helium) .
  • the AICI 3 is sufficiently micropulverized to provide a first order rate constant, after activation, of at least 0.10 minute -1 at boiling •under reflux conditions.
  • the weight ratio of chloro- fluorocarbon used during activation to micropulverized anhydrous aluminum trichloride is typically from about 10:1 to about 300:1, is preferably from about 20:1 to 70:1, and is most preferably about 50:1.
  • the aluminum trichloride is preferably activated at a temperature within the range of from about 7°C to about 52°C when CFC-113 is used.
  • CFC-113 e.g., a mixture of micropulverized AICI 3 and CCI 2 FCCIF 2 may be heated to boil under reflux (about 48°C) for four hours with stirring.
  • Overheating due to rapid reaction of CFC-113 can be controlled during activation by using CFC-113a (e.g., a ratio of CFC-113a to CFC-113 of about 1.5:1) as a heat sink and diluent to limit the reaction rate.
  • the mixture may then be cooled with stirring to 20°C, at which point the stirring is stopped.
  • the supernatant liquid may be decanted from the reaction vessel.
  • a small amount of chlorofluorocarbons typically between about 10 to about 20 weight percent is generally retained as a slurry with the activated catalyst.
  • the activated aluminum trihalide derivative is contacted with additional CCI 2 FCCIF 2 for isomerization. Typically, stirring is employed during catalyst contact.
  • a catalyst slurry containing the activated catalyst may be transferred to a new reaction vessel for the isomerization, or the additional CCI 2 FCCIF2 to be isomerized may be added directly to the vessel containing the freshly activated catalyst.
  • the reaction vessel(s) used for catalyst activation and isomerization may be any chemically resistant material such as glass (e.g., glass-lined reactors) or carbon steel. Reactor materials which leach contaminants such as undesirable metals into the • reaction mixture are preferably avoided.
  • the isomerization is initially conducted with stirring at a temperature of at least about 47°C.
  • the initial temperature is from about 47°C to 52°C (i.e., at or near the boiling temperature for CCI 2 FCCIF 2 ) .
  • the reaction mixture is cooled to about 20°C, and the isomerization is terminated when the amount of CCI2FCCIF2 in the reaction vessel is less than 400 ppm, preferably, especially for commercial production, about 350 ppm or less (e.g., about 320 ppm).
  • the catalyst activity, the reaction temperature and the catalyst concentration are preferably controlled so that the desired degree of isomerization is acheived in from about 0.25 to about 4 hours, most preferably about 0.5 hours.
  • the catalyst may be reused until its activity becomes undesirably low.
  • the catalyst may be reused by adding to the slurried catalyst an amount of fresh chlorofluorocarbon approximately equal in weight to the product mixture removed.
  • the weight ratio of chlorofluorocarbon to the original aluminum trichloride catalyst used in each batch is typically between about •30:1 to about 70:1. Separation of the products from the organic phase can be done collectively using a pool of organic phases recovered from a series of isomerizations, or singularly upon the removal of product mixture from the settled catalyst.
  • Catalyst life can be as important commercially as the rate of the reaction. Surprisingly, the lifetime of catalysts, as indicated by the number of batch runs that a catalyst can be used to produce product within specification (e.g., less than about 400 ppm CFC-113 at 20°C) , increases with the surf ce area of the micro ⁇ pulverized catalyst precursor.
  • the catalyst of this invention can be used to isomerize at least about 500 kg of CFC-113 per kg of AICI 3 .
  • the isomerization rate prior to cooling (e.g., prior to cooling from an initial isomerization temperature of about 47°C or more) is typically at least about 10 kg of CFC-113 per kg of AICI 3 per hour.
  • the catalyst When used during isomerization in a weight ratio up to about 50 g CFC-113 per g AICI 3 (e.g., 20 to 40 g CFC-113/g AICI 3 ) the catalyst is preferably used for at least about 30 isomerization cycles (i.e., isomerization of 30 batches of fresh CCI 2 FCCIF 2 ) ; most preferably, especially for commercial production, at least about 70 isomerization cycles (e.g., about 140 cycles, or even more) .
  • isomerization cycles i.e., isomerization of 30 batches of fresh CCI 2 FCCIF 2
  • 70 isomerization cycles e.g., about 140 cycles, or even more
  • the catalyst is used to isomerize at least about 1000 kg CCI 2 FCCIF2 per kg of AICI3, most preferably, especially for commercial production, at least about 4000 kg CCI 2 FCCIF 2 per kg AICI 3 (e.g., about 5000 kg CCI 2 FCCIF 2 per kg AICI 3 , or more) .
  • the isomerization rate of CCI 2 FCCIF 2 prior to cooling is at least about 25 kg of said chlorofluorocarbon per kg
  • the isomerization normally proceeds at atmospheric pressure.
  • anhydrous aluminum trichloride and certain chlorofluorocarbons such as CCI 2 FCCIF 2
  • the process may be performed in a suitable pressure vessel. Adequate heat removal to prevent overheating of the catalyst is desirable to achieve the most active, long-lived catalyst.
  • the product produced by isomerization of CCI2FCCIF 2 starting material is a high purity composition of
  • CCI 3 CF 3 (i.e., the product produced consists essentially of CCI 3 CF 3 containing less than about 400 ppm CCI2FCCIF2) .
  • A. Catalyst Activation A 250 mil Erlenmeyer flask was equipped with a hot plate/stirrer. Teflon® (polytetrafluoroethylene) stirring bar. Teflon® sleeves, an inlet port capped with a Teflon®-coated septum, a condenser with a nitrogen inlet tube and a 250 mL addition funnel fitted with a Teflon® stopcock and connected to a Krytox®
  • thermocouple perfluorinated polyether oil bubbler. All the glassware was oven-dried prior to use. The Erlenmeyer flask was flushed with dry nitrogen and capped with a glass stopper. The flask was charged with AICI 3 (1.0 g) in a nitrogen-blanketed dry box. The flask was capped with a glass stopper, removed from the dry box and quickly attached to the reflux condenser purged with N 2 , and the addition funnel. A thin wire (1/32", 0.79 mm) thermocouple was inserted through the septum so that it was located in the vapor space of the reaction (in some experiments, a thermocouple was inserted in a thermowell) . A continuous and generous 2 purge was maintained through the nitrogen inlet.
  • micropulverized AICI 3 samples possessed a particle size such that 80% of the material passed through 100 mesh screen (sieve opening of 0.149 mm) .
  • Surface areas for each of the AICI 3 samples were measured using the standard BET nitrogen sorption method by degassing about one gram (g) of the sample at room temperature using helium flow in a Micromeritics Desorb 2300B system, measuring adsorption and desorption on a Micromeritics Flowsorb II 2300 system with a mixed gas of 30% nitrogen and 70% helium, and calculating the surface area.
  • the first-order rate constant for the conversion of CC1 2 FCC1F 2 (CFC-113) to CCI 3 CF 3 (CFC-113a) was measured for the first isomerization for each sample, and the results are shown in Table 1.
  • the data show that the rates of isomerization are faster for catalyst precursors with higher surface areas.
  • the micropulverized AICI 3 always performed better (i.e., faster) than standard AICI 3 .
  • the modified Erlenmeyer flask described above was flushed (septum attached) with dry nitrogen. While flushing, it was quickly stoppered and placed in a dry box with a glass vial, a wide-bore glass funnel and a scoupula. A small amount of AICI 3 was placed in the vial to coat the internal walls. Some AICI 3 was also used to coat the walls of the funnel. AICI 3 was weighed in the coated glass- vial, and then about 5.4 g was transferred to the reaction flask through the funnel. The flask was quickly stoppered and removed from the dry box.
  • Examples 1 and 2 clearly show that catalysts of this invention are not only highly active (as shown by the rate of isomerization) , but also produce high quality product through numerous batch runs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention se rapporte à un procédé de production de CCl3CF3 par isomérisation catalytique. Selon ce procédé, (1) on active un trichlorure d'aluminium anhydre micropulvérisé, présentant une suface spécifique supérieure à 0,8 m2/g, par traitement à agitation avec au moins 10 g de CCl¿2?FCClF2 par g de trichlorure d'aluminium; et (2) on isomérise une quantité supplémentaire de CCl2FCClF2 en effectuant (i) le mélange à agitation de ladite quantité supplémentaire de CCl2FCClF2 avec ledit catalyseur activé pour produire un niveau initial d'isomérisation, et (ii) le refroidissement à agitation du mélange chlorofluorocarbures/catalyseur à une température d'environ 20 °C, pour obtenir un produit contenant CCl3CF3 et présentant une teneur en CCl2FCClF2 inférieure à environ 400 ppm.
PCT/US1993/006824 1992-07-31 1993-07-23 Procede d'isomerisation de 1,1,2-trichlorotrifluorethane WO1994003417A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69314644T DE69314644T2 (de) 1992-07-31 1993-07-23 Verfahren zur isomerisierung von 1,1,2-trichlortrifluorethan
JP50535094A JP3322402B2 (ja) 1992-07-31 1993-07-23 １，１，２−トリクロロトリフルオロエタンの異性化方法
EP93918272A EP0652857B1 (fr) 1992-07-31 1993-07-23 Procede d'isomerisation de 1,1,2-trichlorotrifluorethane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US92312792A 1992-07-31 1992-07-31
US07/923,127 1992-07-31

Publications (1)

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WO1994003417A1 true WO1994003417A1 (fr) 1994-02-17

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PCT/US1993/006824 WO1994003417A1 (fr) 1992-07-31 1993-07-23 Procede d'isomerisation de 1,1,2-trichlorotrifluorethane

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EP (1) EP0652857B1 (fr)
JP (1) JP3322402B2 (fr)
DE (1) DE69314644T2 (fr)
ES (1) ES2107678T3 (fr)
WO (1) WO1994003417A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545770A (en) * 1993-11-01 1996-08-13 E.I. Du Pont De Nemours And Company Process for manufacture of high purity 1, 1-dichlorotetrafluoroethane
US7600791B2 (en) 2004-09-10 2009-10-13 Emcon Technologies Llc Exhaust system
US8058491B2 (en) 2007-08-16 2011-11-15 E. I. Du Pont De Nemours And Company Catalytic isomerization between E and Z isomers of 1,2,3,3,3-pentafluoropropene using aluminum catalyst
RU2706363C1 (ru) * 2019-06-14 2019-11-18 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Способ получения гем-дихлорциклопентенов
CN110818527A (zh) * 2019-11-19 2020-02-21 常熟三爱富氟化工有限责任公司 反应精馏制备高纯度1,1,1-三氯三氟乙烷的连续工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10322380B3 (de) * 2003-05-17 2005-01-05 Zeuna-Stärker GmbH & Co. KG Abgasanlage
JP2010536777A (ja) * 2007-08-16 2010-12-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー アルミニウム触媒を用いた１，２，３，３，３−ペンタフルオロプロペンのｅ異性体とｚ異性体間での触媒異性化

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1668346A1 (de) * 1967-12-06 1971-04-15 Kali Chemie Ag Verfahren zur Herstellung von 1,1,1-Trifluortrichloraethan
US4925993A (en) * 1989-06-14 1990-05-15 Dixie Chemical Company Process for preparing chlorofluorocarbons via an in situ generated activated aluminum trichloride catalyst and products resulting therefrom

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1668346A1 (de) * 1967-12-06 1971-04-15 Kali Chemie Ag Verfahren zur Herstellung von 1,1,1-Trifluortrichloraethan
US4925993A (en) * 1989-06-14 1990-05-15 Dixie Chemical Company Process for preparing chlorofluorocarbons via an in situ generated activated aluminum trichloride catalyst and products resulting therefrom

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545770A (en) * 1993-11-01 1996-08-13 E.I. Du Pont De Nemours And Company Process for manufacture of high purity 1, 1-dichlorotetrafluoroethane
US7600791B2 (en) 2004-09-10 2009-10-13 Emcon Technologies Llc Exhaust system
US8058491B2 (en) 2007-08-16 2011-11-15 E. I. Du Pont De Nemours And Company Catalytic isomerization between E and Z isomers of 1,2,3,3,3-pentafluoropropene using aluminum catalyst
RU2706363C1 (ru) * 2019-06-14 2019-11-18 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Способ получения гем-дихлорциклопентенов
CN110818527A (zh) * 2019-11-19 2020-02-21 常熟三爱富氟化工有限责任公司 反应精馏制备高纯度1,1,1-三氯三氟乙烷的连续工艺

Also Published As

Publication number Publication date
DE69314644T2 (de) 1998-02-12
EP0652857B1 (fr) 1997-10-15
DE69314644D1 (de) 1997-11-20
EP0652857A1 (fr) 1995-05-17
JPH08500347A (ja) 1996-01-16
JP3322402B2 (ja) 2002-09-09
ES2107678T3 (es) 1997-12-01

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